Telomers which can be cross-linked by light

ABSTRACT

Telomers and cotelomers with at least one sequence which can be cross-linked by light, and a method of preparing them. 
     They are of the general formula ##STR1## wherein the taxogen links --(X i )-- belong to the group made up of 2-hydroxy ethyl acrylate and methacrylate, acrylic or methacrylic acid, vinyl alcohol and allyl alcohol; the ##STR2## links emanate from the same taxogen X i , esterified by means of a group with at least one photo-crosslinkable double bond in its molecule; and where 1&lt;x+y≦1000, Z being chosen form the group --H, --Cl, --Br; and where R may be a simple or macromolecular radical, in the latter case leading to the formation of dual sequence cotelomers. 
     The manufacturing process comprises telomerization by redox or radical catalysis, followed by grafting on the photo-crosslinkable group, the first phase of telomerization being duplicated in the case of a cotelomer. 
     The main application for the products is in coating metals.

The invention relates to telomers with one or more sequences, at leastone of which has unsaturated lateral groups over its length, the lateralgroups being distributed statistically and having properties ofcross-linking by light.

It also concerns a method of obtaining these telomers.

Telomers are synthesised organic substances resulting from a reactionknown as telomerisation, in which an unsaturated organic compound X_(i)called the "taxogen" reacts in the presence of catalysts or initiatorswith another compound AZ called the "telogen", leading to thecondensation of X_(i), in formation of a sequence of n divalent--(X_(i))-- links, and the division of the telogen AZ into two parts,which are hooked onto the ends of the sequence to give a product of thegeneral formula: A--(X_(i))_(n) --Z called the telomer. This may in turnact as a telogenic agent for another taxogen Y_(i) and lead to theproduction of dual sequence cotelomers of the general formula:

    A'--(Y.sub.i).sub.n' --A"--(X.sub.i).sub.n --Z

where A' and A" result from the division of A.

Applicants have taken a particular interest in these products and inderivitives thereof which result from grafting unsaturated lateralgrafts onto at least one of the sequences.

Molecules of low molecular weight which have unsaturated groups arealready known or on the market. For example, in the case of allylgrafts, 1,1,2,2-tetraallyloxy ethane has in fact been commercialised,and in the case of acrylic grafts acrylates of diols, triols or tetraolsare known. But these compounds do not have more than four groups thatcan be photopolymerised.

Molecules of molecular weight from 1000 to 3000 (telechelic oligomers)with two acrylic groups at the ends of the chain are widely used inindustry. These macromolecules may e.g. be obtained from dihydroxylatedpolyurethanes or polyesters.

Finally, polymers of high molecular weight with substituted allyl and/oracrylic groups have been known for a long time, and applications of themstill form the subject of many patents and publications. Some examplesare polyvinyl alcohols and glycol poly(meth)acrylates substituted byacrylic groups of the cinnamic, β-(2-furyl)acrylic or β-(pyridyl)acrylictype. Very few compounds with unsubstituted allyl or acrylic grafts havebeen described in the literature in connection with this type ofmacromolecule. French Pat. No. 2 412 572, in which the grafts are formedby carbonate bridges, should nevertheless be noted.

The originality of the invention stems from the fact that Applicantshave synthesised single sequence telomers and dual sequence telomers orcotelomers with sequences of specific length and have grafted controllednumbers of special groups onto them. This has resulted in new products,with a combination of important properties which can be applied tovarious technical fields.

Thus Applicants have been able to make products with sequences of smalllength, that is to say, of relatively low molecular weight, withconsequent low viscosity and a resultant ability to be used withoutsolvent.

They have also developed single sequence telomers with links of astructure such that a certain number of highly reactive groups, such asacrylic and allyl derivitives, could be hooked onto them, thus givingthem remarkable properties of cross-linking by light, while stillleaving some links in the sequence ungrafted and thus enabling them toapply their own properties, for example enabling links with an acid oralcohol function to have more or less solubility in water or an abilityto adhere to metals.

By extending the invention to dual sequence telomers, Applicants havebeen able to create or develop other properties, depending on what thesecond sequence consists of. Some examples of these properties areimproved surface properties when fluorine radicals are present,flexibility when there are diene radicals or resistance to hydrocarbonswhen working with acrylic radicals such as acrylonitrile.

The telomers according to the invention are of the general formula:##STR3## wherein the sequence of --(X_(i))-- and ##STR4## links emanatesfrom an identical taxogen X_(i) with a free function, belonging to thegroup made up of primary alcohol, acid and secondary alcohol functions,and where the ##STR5## links correspond to the esterified form of X_(i),R' being the radical of the group used for esterification, RCCl₂ -- and--Z being the parts of the telogen RCCl₂ Z where --Z belongs to thegroup made up of the --H, --Cl and --Br radicals and R belongs to thegroup made up of simple radicals and macromolecular radicals,characterised in that X_(i) belongs to the group made up of sub-groupsX₁, X₂, X₃, X₄ in which X₁ is represented by 2-hydroxy ethyl acrylateand 2-hydroxy ethyl methacrylate, X₂ is represented by acrylic acid andmethacrylic acid, X₃ is represented by vinyl alcohol, X₄ is representedby allyl alcohol, that 0<x≦500, 1<y≦500, 1<x+y≦1000, and that the groupused for esterification has at least one double bond which can becross-linked by light and belongs to the group made up of acids and acidchlorides in the case of X₁, X₃ and X₄ and alcohols in the case of X₂.

Thus the telomers claimed are charecterised in particular by thepresence of a sequence where the taxogen has a free function, such asthe primary alcohol function in 2-hydroxy ethyl acrylate andmethacrylate and allyl alcohol, the acid function in acrylic acidmethacrylic acid and the secondary alcohol function in vinyl alcohol.The number of links in the sequence is from 1 to 1000, and all or atleast half of these are esterified by acid or alcohol groups which haveat least one ethylene bond that can be cross-linked by light. The groupsare distributed statistically along the sequence and enable theresultant telomer simultaneously to develop the properties resultingfrom the presence of the various nonesterified functions.

Different groups may be used for esterification, depending on thestructure of the taxogen forming the links of the sequence. Thus wherethe taxogen is X₁ or X₃ or X₄ and has an alcohol function, acrylic,methacrylic, cinnamic, furyl acrylic, cinnamylidene or allyl acid shouldbe chosen. Where the taxogen has an acid function, referred to as X₂, analcohol such as 2-hydroxy ethyl acrylate or methacrylate, allyl alcoholor cinnamic alcohol should be chosen.

Z, which may be a --H, --Cl or --Br radical, is preferably limited tothe --Cl radical when the taxogen is of the X₁ and X₂ type.

As far as R is concerned, it belongs to the group made up of simple andmacromolecular radicals. The macromolecular radicals emanate from othertelomers where Y₁ is the taxogen and thus lead to the formation of dualsequence cotelomers, which enjoy the advantages provided by theproperties of both sequences.

The radical R may take different forms, depending on the taxogen X_(i).

Thus with X₁, R may be a simple radical belonging to the group made upof --Cl, CH₃ --O--CO-- and CF₃ --, corresponding respectively to carbontetrachloride, methyl trichloroacetate and trifluorotrichloroethanetelogens.

R may also be a macromolecular radical belonging to the group made upof: ##STR6## where 1≦n₁ ≦10, ##STR7## where 1≦n₂ ≦500, that is to say,the radicals emanate respectively from the following telomers:chlorotrifluoroethylene-carbon tetrachloride, vinyl acetate-chloroform,vinyl acetate-carbon tetrachloride, methacrylic acid-carbontetrachloride, methyl methacrylate-carbon tetrachloride, isoprene-carbontetrachloride.

With X₂, R may be a simple radical belonging to the group made up of--Cl and --CF₃, corresponding respectively to telogens of carbontetrachloride and trifluorotrichloroethane, and also the macromolecularradical --(CF₂ --CFCl)_(n).sbsb.1 --Cl where 1≦n₁ ≦10, that is to say,the radical emanating from the chlorotrifluoroethylenecarbontetrachloride telomer.

With X₃, R may be the simple radical belonging to the group made up of--Cl, (C₂ H₅ O)₂ --PO-- or a macromolecular radical belonging to thegroup made up of ##STR8## that is to say, the radicals emanaterespectively from carbon tetrachloride, chloroform, diethyl hydrogenphosphonate and bromotrichloromethane telomers and vinyl acetate andisoprene telomers with carbon tetrachloride or chloroform telogens.

With X₄, R may be a simple radical belonging to the group made up of--CCl₂ --CO₂ H, --CCl₂ --CO₂ CH₃, --CCl₃, (C₂ H₅ O)₂ --PO--, that is tosay, emanating respectively from the following telogens: trichloroaceticacid, methyl trichloroacetate, chloroform and diethyl hydrogenphosphonate.

The invention also concerns a method of preparing the telomers andcotelomers described above.

There are generally to main stages:

the first is a process of telomerising the taxogen, which may beduplicated with the telomer obtained being used as the new talogenicagent to obtain dual sequence cotelomers; this is then abistelomerisation process

the second is an esterifying process, in which an unsaturated group,adapted to enable the resultant product to be cross-linked by light, isgrafted onto the links of the sequence of the telomer or onto at leastone of the sequences of the cotelomer.

In some cases, however, esterification may precede telomerisation.

But depending on the taxogen used in telomerisation or that present inthe macromolecular radical R involved in bistelomerisation, thesynthesis of each of these products will take on special features.

Thus in the case of a telomerising reaction, if the taxogen used is ofthe vinyl, conjugated diene or allyl type, the telogenic agent chosenwill be chloroform and catalysis will then be peroxidic (benzoylperoxide or azobisisobutyronitrile then being used to initiatetelomerisation). The cleavage which takes place is the C--H cleavage,and in this case one of the telechelic ends is the trichloromethylgroup: CCl₃.

If the taxogen is of the acrylic, conjugated diene orchlorotrifluoroethylene type, the telogenic agent is then carbontetrachloride and catalysis is of the redox type (the FeCl₃ /benzoincouple is the most commonly used although other transition metals and/ortransition metal salts: Mg, Cu, etc. may also be employed). In thesecases the cleavage of the telogenic agent is of the C--Cl type, but asin the case mentioned above there is still a trichloromethyl group atthe end of the telomer.

In the case of a bistelomerising reaction where the telomers obtainedabove, which are of the RCCl₃ type, then act as telogenic agents, if thenew taxogen is vinylic the reaction will take place by peroxidecatalysis (see above). For all other taxogens: acrylic, conjugateddiene, chlorotrifluoroethylene, catalysis is of the redox type.

Furthermore, when the taxogens are of the vinyl and allyl type, vinylacetate and allyl acetate are used respectively as the base material fortelomerisation. Hydrolysis is then carried out in the presence of sodiummethanolate, leading to the appearance of the alcohol functions ontowhich the groups which can be cross-linked by light will subsequently begrafted.

As far as the number of x+y links included in the various sequences ofthe taxogens is concerned, this is indicated by the average degree ofpolymerisation by number DP_(n) and the index of polydispersity DP_(o)of the telomerising reaction, which are dependent on parameters alreadyknown in the literature.

MAYO has defined a general law for peroxidic telomerisation:

    1/DP.sub.n =1/DP.sub.o +C.sub.T r

and BOUTEVIN and colleagues for telomerisation by redox catalysis:

    1/DP.sub.n =C.sub.cat c+C.sub.T r

with c=(Cata)/(Taxo) and r=(Telo)/(Taxo), C_(T) and C_(cat) being theconstant of transfer to the talogen and to the catalyst.

These laws have been applied in the invention and have made it possiblefor the DP_(n) of the various desired sequences to be determined at aprevious stage. The results obtained in sealed tubes were thenextrapolated onto a semi-industrial reactor for pilot operations. In thereactor it was possible for stages 1 and 2, leading to dual sequencecotelomers, to be carried out in one stage, with the second monomerbeing brought into the reaction when the first stage had come to an end(see example no. 4).

As far as esterification is concerned, various existing methods appliedto simple molecules or polymers have been adapted to dual sequencecotelomers. The methods used depend on the groups to be grafted and thestructure of the taxogens.

Thus, in the case of type X₁, X₃ and X₄ taxogens which thus form polyolsequences, it has been above that the groups used for esterificationwere either acids or acid chlorides.

When they are acrylic acid chlorides such as cinnamic acid chloride, themode of operation used consists of activating with pyridinium complexesor the Schotten Baumann method.

On the other hand, when the groups are acrylic acid one can haverecourse to direct azeotropic esterification, using sulfonic paratolueneacid or sulfuric acid as catalyst. Esterification is effected witharomatic solvent or solvent of the chlorine type: CH₂ Cl₂ or CHCl₃, forexample, when it has to take place at low temperature, due to the dangerof thermal polymerisation.

In the case of X₂ type taxogens, which thus form polyacid sequences,grafting is preceded by activation of the acid functions by passing themthrough acid chloride, using pure thionyl chloride with a reflux.Grafting then takes place in tetrahydrofuran or any other aproticsolvent without any water, in a stream of nitrogen.

The invention will be understood better from the examples of itsapplication which are given below without imposing any restrictions onit.

The telomerisation and/or cotelomerisation reactions were carried out insealed tubes or a reactor under pressure, and in cases where the boilingpoints of the taxogens and telogens were high enough, in a pyrex reactorat atmospheric pressure. The structures described in these examples weredetermined by the following analytical methods: centesimal analysis,magnetic proton resonance, chromatography by permeation of gel,measuring viscosity and infra-red spectrophotometry.

EXAMPLE 1 Telomerisation of the taxogen X₁ : 2-hydroxy ethyl acrylatewith the telogen 1,1,1-trifluorotrichloroethane ##STR9##

174 g of 2-hydroxy ethyl acrylate; 281.25 g of CF₃ CCl₃ ; 2.43 g offerric chloride; 3.15 g of benzoin and 200 cc of acetonitrile are placedin a reactor. It is heated with agitation for 12 hours at a temperatureof 115° C. and a pressure of 4.4 bars. When the reaction is over thesolvent is evaporated and 272 g of a viscous product is obtained.

In a separate process the non-reacted taxogen is removed at 20 Torr. Therate of conversion to telomer is 90%. The mono addition compound isdistilled off (boiling temperature: 92° C. at 0.5×10⁻² Torr).

After fractionated precipitation of the reaction medium, the averagedegree of polymerisation of each fraction is determined by centesimalanalysis. This gives the following results:

products soluble in either: DP_(n) ≦5 (3% by weight of total)

products soluble in chloroform: DP_(n) =9 (53% by weight of total)

products soluble in acetone: DP_(n) =11 (26% by weight of total)

products soluble in methanol: DP_(n) =18 (18% by weight of total).

EXAMPLE 2

Esterification of the telomer from example 1 with acrylic acid. Theproduct with DP_(n) =9 is used. The polyol is directly azeotropicallyesterified at 39.5° C. by the excess acrylic acid, in methylene chloride(CH₂ Cl₂), with sulfonic paratoluene acid being used as catalyst. Thefollowing product is obtained after purification: ##STR10##

EXAMPLE 3 Esterification of the telomer from example 1 by cinnamoylchloride

The various fractions obtained in example 1 are grafted with cinnamoylchloride by the following method: freshly distilled pyridine is placedin a flat-bottomed flask with two tubes, fitted with a condensor, abromine funnel and a magnetic agitating system. The cinnamoyl chloride,dissolved in carbon tetrachloride or toluene, is dripped in through thebromine funnel. When all the solution has been added and a milkyprecipitate appears, the telomer dissolved in pyridine is added. Afterhalf an hour's reaction at room temperature the first precipitatedisappears and a second, granular precipitate appears. The pyridineevaporates and a product soluble in chloroform is obtained.

With all the fractions in example 1 approximately 75% grafting is alwaysobtained. In the case of the fraction soluble in chloroform (DP_(n) =9)we obtain a product of the following formula: ##STR11## φ representing abenzene ring.

EXAMPLE 4 Bistelomerisation of 2-hydroxy ethyl acrylate with the CCl₄-isoprene telomer then grafting of acrylic acid.

773 g of 2-hydroxy ethyl acrylate; 103 g of carbon tetrachloride; 683 gof acetonitrile; 10.8 g of ferric chloride and 14 g of benzoin areplaced in a 4.5 l pilot reactor. The reaction is carried out at 110° C.and 4.4 bars for 4 hours, after which the pressure drops (3.5 bars); 907g of isoprene is then added directly. The reaction is continued for 6hours. After evaporation and treatment, 1095 g of dual sequencecotelomer is obtained. Acrylic acid is then grafted as described inexample 2, and the following final product is obtained: ##STR12## i.e. adual sequence 2-hydroxy ethyl acrylate-isoprene cotelomer containingapproximately 45% of acrylic grafts.

EXAMPLE 5 Bistelomerisation of the taxogen X₂ : acrylic acid with thetelomer of carbon tetrachloride and chlorotrifluoroethylene ##STR13##

2.5 moles of acrylic acid (180 g); 0.49 mole of Cl--(CFCl--CF₂)₃.5--CCl₃ (77.5 g); 2.034×10⁻² mole of ferric chloride (3.17 g); 1.95×10⁻²mole of benzoin (4.14 g) and 200 g of butyronitrile are placed in a 1liter pyrex reactor. The reaction takes place for 24 hours with refluxof the solvent. When the butyronitrile has evaporated, the unreactedtelogen is recovered (14.5 g) aand 140 g of product is obtained. Theratio converted to telomer is 50%. Fractionated precipitation produces100 g of solid white substances soluble in acetonitrile (DP_(n) =44) and40 g of solid yellow substances soluble in ether (DP_(n) =11.5).

EXAMPLE 6 Activation of the acid functions of the cotelomer in example 5

The fraction with DP_(n) =11.5 obtained in example 5 is treated asfollows. 27 g of the telomer is placed in a pyrex reactor fitted with acooler. Pure thionyl chloride (SOCl₂) is added. The solution is heatedfor 114 hours with reflux and vigorously agitated (magnetic agitation).When the volatile products have evaporated, 30.3 g of the following isobtained: ##STR14## Thus all the acid functions are converted to acidchloride functions.

EXAMPLE 7 Esterification of the cotelomer from the previous example withcinnamic alcohol

One third by weight of the product obtained in example 6 (10.1 g) isdissolved in anhydrous tetrahydrofuran. The cotelomer and 19.4 g ofcinnamic alcohol are placed in a flask fitted with a cooler, a brominefunnel and a system for bubbling a stream of nitrogen into the solution.The reaction is brought to a temperature of 40° C. and is followed byliberation of the hydrochloric acid produced. When all the acid has beenliberated, the solvent is evaporated and a product of the followingformula is obtained after purification: ##STR15## giving 87% grafting.

EXAMPLE 8 Esterification of the cotelomer from example 6 by allylalcohol

Allyl alcohol (15 g) is grafted onto a second third of the product ofexample 6 (10.1 g) by the method described in example 7. Afterpurification the following product is obtained: ##STR16## giving 71%grafting.

EXAMPLE 9 Grafting of the cotelomer from example 6 with 2-hydroxy ethylacrylate

2-hydroxy ethyl acrylate (33.5 g) is grafted onto the last third of theproduct of example 6 (10.1 g) following the method described in example7, but this time at room temperature. After purification the followingproduct is obtained: ##STR17## giving 43% grafting.

EXAMPLE 10 Bistelomerisation of the taxogen Y_(i) : isoprene with thevinyl acetate-chloroform telomer ##STR18##

6.75 g (2.5×10⁻³ mole) of vinyl acetate-chloroform telomer (DP_(n) =30);6.8 g of 2-methyl 1,3-butadiene (0.1 mole); 0.13 g of ferric chloride;0.17 g of benzoin and 30 cc of acetonitrile are placed in a sealed tube.When the reaction has continued for 12 hours at 90° C., 13.8 g of aviscous product is obtained. This represents 100% conversion tocotelomer.

EXAMPLE 11 Hydrolysis and esterification of the cotelomer from example10 ##STR19##

The product obtained from example 10 is treated with sodium methanolate.Two products are obtained: a substance insoluble in methanol (70% byweight) and a second substance, soluble in methanol and chloroform (30%by weight). Cinnamoyl chloride is grafted onto these two products by themethod described in example 3. 100% grafting and products of thefollowing formulae are obtained: ##STR20##

EXAMPLE 12 Bistelomerisation of acrylic acid-carbon tetrachloridetelomer with isoprene ##STR21##

12.2 g of ##STR22## (4×10⁻³ mole) synthesised as in example 5 but usingcarbon tetrachloride as the telogenic agent and acetonitrile as thesolvent; 10.88 g of isoprene (0.16 mole); 0.195 g of ferric chloride(1.25×10⁻³ mole); 0.262 g of benzoin (1.25×10⁻³ mole) and 100 cc ofacetonitrile are placed in a glass tube. 18.2 g of product is obtained,representing 55% conversion to telomer. 6 g of the product is soluble inether and 12 g insoluble. There are thus products of the followingformulae: ##STR23##

EXAMPLE 13 Esterification followed by telomerisation

Cinnamoyl chloride is grafted onto 2-hydroxy ethyl acrylate as describedin example 3. The following monomer is obtained: ##STR24## with a 90%yield. The product (24.2 g) is then reacted in a pyrex reactor with 15.4g of carbon tetrachloride; 1.62 g of ferric chloride; 2.12 g of benzoinand 50 cc of acetonitrile. The reaction takes 24 hours with theacetonitrile at reflux. 27 g of product of the following formula isobtained: ##STR25##

EXAMPLE 14 Telomerisation of allyl acetate

2 molar % of benzoyl peroxide, one mole of allyl acetate and r moles oftelogen dissolved in 300 ml of benzene are placed in a 1 liter reactor.When the monomer has been removed (evaporation and washing withpetroleum ether) a viscous product is obtained (yield 80%). The DP_(n)of the product, as a function of r and the telogens used, are given inthe following table:

    ______________________________________                                         ##STR26##                                                                      r      HPO(OEt).sub.2                                                                             HCl.sub.2 CCO.sub.2 CH.sub.3                                                             CCl.sub.3CO.sub.2 CH.sub.3                   ______________________________________                                        1    2.4          3.45         --                                             0.5  4.5          5.9          2.6                                            0.25 8.5          12.5         5                                              0.2  10           13.5         6.3                                            ______________________________________                                    

EXAMPLE 15 Esterification of the telomers of allyl acetate

The products obtained in example 14 are treated in the same way as inexample 11. The corresponding telomers which can be cross-linked bylight are obtained with 100% grafting.

Owing to their properties of water solubility, encrophilia, flexibility,adhesion to metals and resistance to oils, the cross-linkable telomersand cotelomers according to the invention have applications both inprinting (manufacture of offset plates, photogravure and flexographicprinting) and in the production of certain computer or microprocessorcomponents (printed circuits) and as coating agents for certainmetallurgical products.

We claim:
 1. Telomers of the general formula ##STR27## wherein thesequence of ##STR28## links emanates from an identical taxogen X_(i)with a free function, selected from the group consisting of primaryalcohol, acid and secondary alcohol functions, and where the ##STR29##links correspond to the esterified form of X_(i), R' being the radicalof the group used for esterification, RCCl₂ -- and --Z being the partsof the telogen RCCl₂ Z where --X is selected from the group consistingof --H, --Cl and --Br radicals, wherein X_(i) belongs to the group madeup of sub-groups X₁, X₂, X₃, X₄ in which X₁ is selected from the groupconsisting of 2-hydroxy ethyl acrylate and 2-hydroxy ethyl methacrylate,X₂ is selected from the group consisting of acrylic acid and methacrylicacid, X₃ is vinyl alcohol, X₄ is allyl alcohol, 0<x≦500, 1<y≦5001<x+y≦1000, wherein the group used for esterification has at least onedouble bond which can be cross-linked by light and is selected from thegroup consisting of acids and acid chlorides in the case of X₁, X₃ andX₄ and is an alcohol in the case of X₂ and wherein X_(i) is X₁, R isselected from the group consisting of Cl, CH₃ OCO, CF₃, --(CF₂--CFCl)_(n).sbsb.1 --Cl where 1≦n₁ ≦10, ##STR30## where 1≦n₂ ≦500; whenX_(i) is X₂, R is selected from the group consisting of Cl, CF₃ and (CF₂--CFCl--_(n).sbsb.3 Cl where 1≦n₃ ≦10; when X_(i) is X₃, R is selectedfrom the group consisting of Cl, (C₂ H₅ O--₂ PO, ##STR31## where 1≦n₄<500; and when X_(i) is X₄, R is selected from the group consisting ofCCl₂ --CO₂ H, CCl₂ --CO₂ CH₃, CCl₃ and (C₂ H₅ O--₂ PO.
 2. The telomersof claim 1, wherein the group used to esterify X₁, X₃ and X₄ is selectedfrom the group consisting of the following acids: acrylic, methacrylic,cinnamic, furyl acrylic, cinnamylidene and allyl.
 3. The telomers ofclaim 1, wherein the group used to esterify X₂ is selected from thegroup consisting of 2-hydroxy ethyl acrylate and methacrylate, allylalcohol and cinnamic alcohol.
 4. The telomers of claim 1, wherein whenthe taxogen is of the type X₁ and X₂, the radical --Z is --Cl.
 5. Thetelomers of claim 1, wherein when the taxogen is of the type X₁, R is asimple radical selected from the group consisting of --Cl, CH₃ --O--CO--and CF₃ --.
 6. The telomers of claim 1, wherein when the taxogen is ofthe X₁ type, R is a macromolecular radical selected from the groupconsisting of: --(CF₂ --CFCl)_(n).sbsb.1 --Cl where 1≦n≦10, ##STR32##where 1≦n₂ ≦500.
 7. The telomers of claim 1, wherein when the taxogen isof the type X₂, R is a simple radical selected from the group consistingof --Cl and --CF₃.
 8. The telomers of claim 1, wherein when the taxogenis the type X₂, R is the macromolecular radical --(CF₂--CFCl)_(n).sbsb.1 where 1≦n₁ ≦10.
 9. The telomers of claim 1, whereinwhen the taxogen is of the type X₃, R is a simple radical selected fromthe group consisting of --Cl and (C₂ H₅ O)₂ --PO--.
 10. The telomers ofclaim 1, wherein when the taxogen is of the X₃ type, R is amacromolecular radical selected from the group consisting of ##STR33##where 1≦n₂ ≦500.
 11. The telomers of claim 1, wherein when the taxogenis of the type X₄, R is a simple radical selected from the groupconsisting of --CCl₂ --CO₂ H,--CCl₂ --CO₂ CH₃,--CCl₃ and (C₂ H₅ O)₂--PO--.
 12. The telomer of claim 1, defined by the following formula:##STR34##